Foaming detergent compositions



United States Patent 2,941,951 FOAMING DETERGENT {IGMPQSETIONS Charles F. Jelinek, Easton, Pa., and Raymond L. Mayhew, Phillipsbnrg, N.J., assignors to General Aniline & Fiirn Corporation, New York, N.Y., a corporation of Delaware No Drawing. Filed May 27, 1955, $63. No. 511,758

16 Claims. or. 252-461) This invention relates to improved foaming detergent compositions and more particularly to improved foaming detergent compositions of the unbuilt or light duty type.

Considerable research has been carried out during the past few years directed towards improving the detersive and foaming properties of the new synthetic detergent compositions. Most of these synthetic detergent compositions have as the active detersive ingredient an anionic atoms. As representative of the various additives which have been employed for improving the detersive and foaming properties of such anionic detergent compositions, there may be mentioned alkali metal phosphates, borates, carbonates, sulfates, chlorides, silicates, higher aliphatic alcohols such as lauryl alcohol and higher fatty acid amides and alkylol amides such as lauroyl amide, lauroyl monoand dialkyl amides, lauroyl ethanolamide, and lauroyl diethanolamide. The use of the aforementioned alkali metal salts, particularly the phosphates and borates, generally results in what are known as built or heavy duty type detergents. While such detergent compositions are highly suitable for use in cleansing machines of various types, they find limited use in applications wherein any substantial amount of contact with the skin is involved, in view of their alkaline reaction and chemical nature. For the latter type of use, unbuilt or light duty type detergent compositions of a substantially neutral reaction are accordingly preferred. However, those foaming and detersive additives which have thus far been more or less commercially accepted have properties and characteristics which could be much improved with respect to more universal compatibility and adaptability to different conditions, cost and thelike.

It is an object of this invention to provide an improved foaming unbuilt or light duty detergent composition. It is another object of this invention to improve the detersive, foam generating and/0r foam stability properties of the presently known unbuilt or light duty synthetic detergent compositions. Other objects and advantages will appear as the description proceeds.

The above objects are attained by the instant invention which is based upon the discovery that the detersive, foam generating and/ or foam stability properties of light duty synthetic detergent compositions containing a sulfate ester of a polyoxyethylenated organic compound and, optionally, an alkyl aryl sulfonate as the active detersive ingredient are unexpectedly improved by addition thereto of a polyoxyethylene ether of a multi-branched chain primary aliphatic alcohol of from about 8 to 18 carbon atoms containing, by weight, about 50 to 90 percent of combined ethylene oxide, said alcoholhaving the molecular configuration of an alcohol produced by the 0x0 process from a multibranched olefin of from 7 to 17 carbon atoms. The instant invention accordingly re sides in the provision of a foaming detergent composition comprising about 25 to 75 parts of a detersive watersoluble anionic sulfate ester of a polyoxyethylene derivative of an organic compound of at least carbon atoms, about 75 to 0 parts of a water-soluble anionic alkyl aryl 2,941,951 Patented June 21,

sulfonate 'detergent containing at least 8 alkyl carbon atoms, and about 1'0 t0'9'0% of the combined 'weightof said anionic detergents of a non-ionic surface active polyoxyethylene ether of a multi-branched chain primary aliphatic alcohol of from a bout 8 to 18 carbon atoms containing, by weight, about 50 to of combined ethylene oxide, saidalcohol having the molecular configurationof an alcohol produced by the Oxo process from a multi-branched olefin of from 7 to 17 carbon atoms.

In the production of the non-ionic polyoxyethylene ethers employed as additives in the instant invention, the following multi-branched chain aliphatic alcohols are mentioned by way of example only as suitable for ethoxylation: 2,4,5,5,7-pentamethyl-l-octanol, 2,3,5,7-tetramethyl-1-nonanol, 3,5-diethyl-1-octanol, 2,4,7-trimethyl- 1- nonanol, 2,4,5,6,8-pentamethyl-l-nonanol, 2,6,7-trimethyl- 3-ethyl-l-octanol, 2,4,6,8-tetramethyl-l-nonanol, 2,4,5-trimethyl-4,7-diethyl-l-octanol, 2,3,5,6-tetramethyl- 5,7-diethyl-1-octanol, 3,5-dimethyl-4,6-diethyl-l-heptanoi, 3,4,5 trimethyl-2,6-diethyl-l-heptanol, 2 ethyl- 3,5,7 trimethyl-l-oc-tanol, 2-ethyl-4,6-dimethyl-l-octanol, 4-.butyl- Z-methyl-l-octanol, 2,5,7,7-tetramethyl-l-octanol, 3,5,7,7- tetramethyl-l-octanol, 2,5-diethyl-3,7-dimethyl-l-octanol, and 2,5,7,9-tetramethyl-1-decanol. Preferably, alcohols are employed which have been produced by the 0x0 process from a multi-branched olefin of 7 to 17 carbon atoms. Such olefins may be prepared by the reaction and/or polymerization of propylene, isobutylene, or the like ormixtures thereof. Thus, an olefin such as tripropylene, tetrapropylene, .pentapropylene, diisobutylene, triisobu-tylene, tetraisobutylene, tributene, 4,6,8 trimethyl-l-nonene, 4,6,8-trimethyl-2-nonene, mixed propene-butene polymers, the reaction product of propylene and isobutylene, 5,7,7- trimethyl-l-octene, 3,5,7-trimethyl-l-heptene, and/or 2,4, 6,6,8-pent'amethyl-l-nonene may be catalytically reacted with carbon monoxide and hydrogen to form the CO1- responding aldehyde, followed by catalytic reduction of this aldehyde to the corresponding primary alcohol. This two stage process is known as the 0x0 process, and always yields in a major proportion of branched chain products according to Storch, 'Golumbic, and Anderson (The Fischer-Tropsch and Related Syntheses, chapter 5, page 441, John Wiley and Sons, New York, 1951). The Oxo reaction always results in the addition of a -CH OH group at the unsaturated bond of the olefin whereby the resulting alcohol .contains one more carbon atom, and usually one more branched chain, than the corresponding olefin. It will be understood that similar alcohols :may be produced from the above-mentioned olefms by other p-rocesses, .as for example by conversion of the hydrogen bromide addition product of the olefin to the corresponding Grignard reagentby reaction. with metallic magnesium, and reaction of the said Grignard reagent with formaldehyde,.followed by acid hydrolysis to the corresponding alcohol.

The above-mentioned multi-branched chain primary aliphatic alcohols must be reacted withthe required number of moles of ethylene oxide to produce the nonionic polyoxyethylene ethers employed in the instant invention. This oxyethylenation reaction is well known in the art and is fully described in U.S Patent No. 1,970,578 and many other patents. The reaction is preferably carried out atelevated temperatures and pressures and may be catalyzed by quaternary hydroxides, amines, acids and/ or coordinating type compounds although strong alkaline catalysts such as KOH or NaOH and the like are preferred because of the fewer by-products formed and the more easily controllable reaction conditions. Since the reaction is substantially quantitative, the molecular proportions of ethyleneo'xide and alcohol employed determine the average oxyethylene chain length of the resulting polyoxyethylene ether, although it will be understood that the product is a mixture of polyoxyethylene ethers of varying oxyethylene chain length. As stated above, sufficient ethylene oxide is employed to produce a polyoxyethylene ether containing by weight about 50 to 90 percent of-cornbined ethylene oxide. The optimum oxyethylene chain length will in any particular instance be determined mainly by the particular alcohol being oxyethylenated, the particular anionic detergent with which it is to be admixed, the hardness of the water in which the detergent is to be employed, and the like. In general, to maintain proper balance in the polyoxyethylene ether, the polyoxyethlene chain length should vary directly with the molecular weight of the alcohol, within the stated range.

The preferred polyoxyethylene ether for use in the instant invention is the' polyoxyethylene ether of Oxo tridecyl alcohol, which alcohol may for example be produced by the x0 process from tetr'apropylene or triisobutylene. The reaction products of 0x0 tridecyl alcohol with from 5 to 30 moles of ethylene oxide are outstandingly effective in light duty detergent compositions based on the use of the above-mentioned anionic detergents as the active ingredient.

These non-ionic polyoxyethylene ethers maybe represented by the following formula:

wherein R is a multi-branched chain alkyl group of 7 to 17 carbon atoms, and n represents the number of ethoxy groups sufiicient to constitute, by weight, about 50 to 90 percent of the non-ionic compound. It will be understood that propylene oxide may in some cases be substituted for part of the ethylene oxide for oxyalkylating the above described multi-branched chain primary aliphatic alcohols for use in the instant invention.

Esters of polyoxyethylenated organic compounds operative as detergents in the instant invention are also well known in the art, being generally produced by reacting a plurality of moles of ethylene oxide with an organic compound containing at least 10 carbon atoms and a reactive hydrogen atom, followed by subjecting the resulting polyoxyethylenated derivative to esterification with a strong acid such as chlorosulfonic, sulfamic, sulfuric or phosphoric or with an organic acid anhydride such as sulfur trioxide or phosphorus pentoxide or with acid halides such assulfuryl chloride, phosphorus oxychloride, or phosphorus pentachloride or the like. Particularly advantageous results have been obtained with the sulfate esters. When a properly substituted acid mixture is employed in the esterification such as aminosulfonic acids, sulfamicacid, ammonium bisulfate, and the like, a watersoluble or dispersible salt is directly produced without the necessity of subsequent neutralization with a basic substance. In such cases, subsequent treatment with basic materials is only for the purpose of neutralizing excess acid, and the like. Excellent results are also obtained when complexes of some of the above acids and anhydri-des are employed; For example, a combination of sulfur trioxide or chlorosulfonic acid with an ether such as dioxane, thioxane or fi,,B'-dichlorodiethylether, or with a tertiary nitrogen base such as pyridine or triethylamine may be used. The resulting esters may be neutralized with a basic material such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium acetate, ammonium hydroxide, ammonia, calcium oxide and hydroxide, magnesium oxide and hydroxide, strontium hydroxide, ethanolamine, diethanolamine, triethanolamine, isopropanolamine, amine, trimethylamine,ethylamine, triethylamine, diethylamine, butylamine, propylamine, isopropylamine, cyclohexylarnine, morpholine, pyridine, octanolamine, octylamine, and the like, to produce the corresponding alkali metal, alkaline earth metal, or ammonium salts. As compounds containing a reactive hydrogen "atom methylamine, dimethyl- 4 there may be mentioned alcohols, phenols, thiols, primary and secondary amines, carboxylic and sulfonic acids and their amides. The amount of ethylene oxide reacted with the reactive hydrogen containing compound, i.e., the length of the polyoxyethylene chain, will depend primarily upon the particular compound with which it is reacted, the maintenance of a proper balance usually requiring increased amounts of ethylene oxide with higher molecular weight reactive hydrogen containing compounds.

The preferred reactive hydrogen containing compounds from which the instant sulfate or phosphate esters are derived are alkyl phenolic compounds. Numerous polyoxyethylenated phenolic compounds containing one or more alkyl substituents are described in U.S. Patents 2,213,477 and 2,593,112. Those perferred are the polyoxyalkylene derivatives of alkyl phenolic compounds in which the total number of alkyl carbon atoms is between 4 and 20. As examples of such phenolic compounds may be mentioned normal and isomeric butyl, amyl, dibutyl and diamyl phenols and cresols, tripropyl phenols and cresols, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, cetyl', oleyl, octadecyl and the like, phenols and cresols, in addition to dihexyland trihexyl-phenol prepared from hexene-l and phenol, diisoheptyl-phenol, dioctyl-phenol, dinonyl-phenol, dioctyl-p-cresol, di-octyl-o-cresol, didecylphenol, didecyl-p-cresol, didodecyl-phenol, and the like. Of particular value are the polyoxyal-kylene derivatives of secondary and tertiary alkyl substituted phenols and cresols obtained by condensing olefins of the type obtained in petroleum refining with phenols or cresols. In the case of products obtained by condensing phenol or cresol with olefins of from 3 to 5 carbon atoms such as propylene, butylene and amylene, it is desirable to employ the dialkylated phenols or cresols, while in the case of compounds obtained by condensing a phenol or cresol with an olefin containing 8 or more carbon atoms, the mono-substituted derivatives are preferred. Particularly desirable derivatives can be obtained from the phenols and cresols containing a substituent derived from olefins containing from 8 to 18 carbon atoms, such as diisobutylene and other alkylenes as nonylene, decylene, undecylene, dodecylene, pentadecylene, octadecylene and mixtures thereof, and may advantageously be the dimers and trimers obtained by polymerization of such low molecular weight olefins as propylene, butylene', isobutylene, amylene or mixtures thereof. However, the polyoxyalkylene derivatives of other organic compounds containing an active hydrogen may be employed in the compositions of the present invention. Thus, the polyoxyalkylene derivatives, described in U.S. Patent 1,970,578, of aliphatic organic hydroxy compounds, 'carboxy compounds and amino compounds, as well as phenolic compounds, may be employed if desired. As examples of water-insoluble higher fatty acids whose polyoxyalkylene derivatives may be employed may be mentioned lauric, oleic, ricinoleic, palmitic and stearic acid, and the like, or mixtures thereof, such as the mixtures obtained from animal and vegetable fats and oils or by the oxidation of such petroleum fractions as paraffin wax. There may also be employed polyoxyalkylene derivatives of water insoluble aliphatic hydroxy compounds 'such as higher aliphatic alcohols, i.e. the Oxo alcohols previously described or the alcohols corresponding to the fatty acids specified immediately above, particularly the alcohols obtainable by hydrogenation of the fatty acids or glycerides present in animal or vegetable oils and waxes such as cocoanut oil, castor oil and the like, as well as the polyoxyalkylene derivatives of the animal and vegetable oils, fats and waxes themselves. There may also be used polyoxyalkylene derivatives of organic mercapto compounds such as the products described in U.S. Patent 2,205,021, i.e., the polyoxyalkylene derivatives of such mercapto compounds as dodecyl mercaptan, oleyl mercaptamcetyl mercaptan, decyl merca'pt'an and 'thiophenols, thionaph;

thol's, benzo-mercaptan, etc.; also the polyox-yalkylene derivatives, such as those described in US. Patent 2,085,- 7 06, of carboxylic acid amides and of sulfonamides of the type described in US. Patent 2,002,613, or the polyoxyal'kylene derivatives, described in US. Patent 2,266,- 141, of sulfonic acids may be employed if desired. Similarly, the surface active polyoxyalkylene derivatives disclosed in US. Patent 2,677,700 may also be employed in the instant invention.

The aforementioned polyoxyethylenated derivatives may then be esterified to produce the corresponding phosphate, or preferably sulfate esters in the manner described hereinabove. These sulfate esters may accordingly be represented by the formula wherein R represents the residue of an organic compound containing a reactive hydrogen atom; 11 represents the member of ethoxy groups sufficient to constitute, by weight, about 20 to 90 percent and preferably about 30 to 65 percent of the anionic compound; M is selected from the group consisting of H, alkali metal, alkaline earth metal, and ammonium; and m is /2 or 1. It will be understood that propylene oxide may be regarded as the equivalent of ethylene oxide for the oxyalkylation of reactive hydrogen containing compounds useful in the production of the phosphate and sulfate esters operative herein as above described. It will also be understood that the term ammonium in the above definition of M embraces the unsubstituted cation derived from ammonia and the substituted cations derived from any of the abovementioned primary, secondary and tertiary amines.

Anionic alkyl aryl sulfonate detergents operative in the instant invention are well known in the art and are generally produced by sulfonation of alkyl aryl compounds. In these compounds, the aryl radical may be mono-nuclear such as benzene, or poly-nuclear such as naphthalene, and is substituted by at least one alkyl group, which may be branched or straight, of at least 4, and preferably from 8 to 20 carbon atoms. The alkyl aryl compound may be monosulfonated or polysulfonated although the best balance for detergent properties is usually attained with one sulfonic acid group. These alkyl aryl sulfonates, though sometimes employed in their free form, are more usually employed in the form of their water-soluble alkali metal salts, e.g., sodium or potassium, although other salts may be used, such as those of the alkaline earth metals, ammonia, and amines mentioned above in connection with the esters of polyoxyethylenated organic compounds. As representative of commonly known alkyl aryl sulfonates operative herein, there may be mentioned sodium dodecylbenzene sulfonate, cyclohexylammonium dodecylbenzene sulfonate, ammonium dodecylbenzene sulfonate, sodium diisobutylbenzene sulfonate, sodium octadecylbenzene sulfonate, sodium diisobutylnaphthalene sulfonate, sodium kerylbenzene sulfonate, sodium octylbenzene sulfonate, sodium dodecylnaphthalene sulfonate, and the like. In general, these alkyl aryl sulfonates may be represented by the formula i al so M) (Rbhy-E J 3 n2 wherein R is an alkyl radical of atleast 4 carbon atoms; R is an alkyl radical; n has a value of 0 to 3; the sum of the carbon atoms in R and (R is at least 8; Ar is selected from the group consisting of benzene and naphthalene; M is selected from. the group consisting of H, alkali metal, alkaline earth metal and ammonium; and 21 has a value of 1 to 2. In this formula, R may be butyl, isobutyl, amyl, and similar normal and branched chain alkyl radicals up to octadecyl and the like, R may represent methyl and ethyl in addition to any of the va ues given r Ra h Pr e re ky r opatss for use in the instant invention are the water-soluble salts, such asthe sodium, ammonium, and amine salts,

of dodecylbenzene sulfonic acid.

The compositions of this invention, may be employed in a dry state, usually inparticulate form, where possible. and advisable. However, since many light duty, deter and foaming properties, of said anionic detergents, is their solubilizing effect thereon. Accordingly, the. instant invention enables the formulation of detergent solutions containing the mixtures described above in concentrations as high as 60 percent by weight, concentrations of about 20' to 60 percent being usually preferred for most purposes. In preparing these concentrates any suitable solvent for the mixture of anionic detergent and non-ionic polyoxyethylene ether may be employed whichis chemically inert thereto, is water-miscible or water-soluble, possesses reasonably good stability to heat, light, chilling and the like, and has a relatively low viscosity in orderto impart to the concentrate the proper fluidity. Suitable solvents include water, low molecular weight alcohols such as ethyl alcohol, propyl alcohol, isopropyl alcohol, ethylene glycol, propylene glycol, glycerol, monomethyl ether of ethylene glycol, monoethyl ether, of ethylene glycol, diethylene glycol, monomethyl ether. of diethylene glycol, monoethyl ether of diethylene glycol, monobutyl ether of diethylene glycol, dioxan, and mixtures thereof. Among the alcohols, aliphatic monohydric and dihydric alcohols are preferred, particularly ethyl and isopropyl alcohol, and their mixtures with water.

As has been pointed out above, the instant compositions contain an anionic sulfate ester of a polyoxyethylene derivative of an organic compound of at least 10 carbon atoms and a non-ionic additive as defined. above, and optionally an alkyl aryl sulfonate detergent, in the proportions specified hereinbefore. While a mixture of said anionic sulfate ester and said non-ionic additive has better foaming and/or detergent properties then either of the components thereof, the improvement in such properties is not as much as could be desired in water of increasing hardness. As one of the features of this invention, it has been found that substitution of part of the said sulfate ester by the alkyl aryl sulfonate as described, results in the attainment of further improved results when employed in water of increasing hardness as, for example, from about 50 p.p.m. (Easton, Pennsylvania, tap water) to 300 p.p.m. (parts per million) hardness. In general, for the three-component system, the sulfate ester and the alkyl aryl sulfonate may be admixed. in any desired proportions, although approximately equal amounts of each of these anionic detergents are usually preferred. The non-ionic additive is employed in proportions of about 10 to by weight of the said sulfate ester, in the twocomponent system, and about 10 to 90% ofthe combined weight of the said sulfate ester and alkyl aryl sulfonate in the three-component system, although generally about 25 to 50% of the combined weight of said anionic detergents is preferred. The resulting detergent compositions are employed in the usual concentrations for washing, which may be from about 0.01 to-5% concentrations in' the wash water.

It will be understood that mixtures of non-ionic additives and of the anionic detergents of the type fully described above may be employed in formulating light duty detergent compositions in accordance with the instant invention. It will also be understood that many factors and variables should be considered by the worker skilled in the art practicing the instant invention in order to achieve optimum results in any particular instance. Among such factors and variables are the nature of the non-ionic additive, the nature of the anionic detergents, their proportions within the range specified above, the

hardnessof the water in which the detergent is to be employed, the manner in which it is to be treated and/or employed, and the like.- For example, for any particular multi-branched chain primary aliphatic alcohol employed in the production of the above-described non-ionic additives, it'will be generally found that, within limits, improvement in the solubility of the resulting detergent composition (with respect to preparation of concentrates, lowering of cloud point on chilling, etc.) varies directly with the proportion of ethylene oxide in the additive. In some cases, highly satisfactory results are achieved by employing one of the known additives such as lauroyl diethanolamide together with the non-ionic additive of the instant invention for admixture with the anionic detergent.

Ingeneral, the compositions of the instant invention enable the production of a higher volume of foam, a higher degree of foam stability and/or a thicker and creamier foam than is attainable by the use of either of the components thereof. In many cases, detersive properties are also improved, particularly in hard water. Thus, tests conducted by applicants have shown that two detergents having the same foam endpoint may have entirely different detergent endpoints and that generally speaking most detergents stop washing dishes clean before the foam endpoint is reached. The above mentioned anionic detergents appear to have particularly poor detergent endpoints. Y i

Compositions in accordance with the instant invention containing the above described non-ionic additive are much improved with respect to detersive endpoints, approaching and in some cases equalling the foam endpoint. This is highly desirable from the consumers viewpoint since the disappearance of foam then serves as an indication of the cessation of detergent action.

The following table shows the results of hand dish washing foaming and detergent tests carried out at a concentration of 0.05% of anionic detergent or non-ionic additive or mixture thereof, in waters-of 10 p.p.m., and 50 p.p.m. and 300 p.p.m. hardness, with varying ratios of anionic detergent to non-ionic additive and varying proportions of ethylene oxide in thenon-ionic additive. The test consisted in washing by hand ordinary glazed porcelain dishes each smeared with approximately 2 Table Foam Endpoint Detcrsive Endpoint Ex. Surfactant No.

10 50 300 10 300 p.p.m. p.p.m. p.p.m. p.p.m. p.p.m.

orbit-r3 no...

.DA 10 70% NH, 30%

TDA n; s

40% NPS, 40%

DBS, 207 OTDA +7 E.O ll 46% NPS, 40% DBS, 20% O'TDA +10 ED 40% NPS, 40%

D138, 20% OTDA ED; 40% NPS, 40%

,DBS, ODA' tion.

grams of an'artificial soil containing Crisco (hydro genated cotton-seed oil) and 20% flour mixed with a small quantity of carbon black and an ultraviolet-responsive' dyestuff under controlled conditions of temperature the washing cycle the dishes stopped being cleaned. This detersive endpoint is also indicated in the table. It will be understood that all parts and proportions mentioned herein and in the appended claims are by weight unless otherwise indicated. v.

In the table, the term DBS means dodecylbenzene sulfonate, sodium salt. The term NPS means nonylphenoxy tetraethyleneoxy sulfate, ammonium salt. The term OTDA means Oxo tridecyl alcohol, the term ODA means Oxo decyl alcohol, obtainable from tripropylene by the 0x0 process, and the terms appearing thereafter refer to the number of moles of ethylene oxide reacted therewith. Examples 1 through 10 of the table show the results of tests on the various components of the compositions of the instant invention, and Examples 11 through 18 show the results of tests carried out on compositions made in accordance with the instant inven- It will be seen from the table that for any given water-hardness, the compositions of the instant invention have improved properties with respect to foaming and/or detergency as compared with the components thereof. Attention is particularly directed to Example 17, the composition of which has identical foam and detersive endpoints in both soft and hard water. As pointed out above, this relationship is highly desirable, particularly from the viewpoint of the consumer. Further, the increase in detergent action is itself a tremendous advance is particularly advantageous in the formulation of compositions which will not be affected by clouding or the like by a drop in temperature during storage, shipping, or the like. A detergent solution in accordance with the instant invention containing 16 parts of ammonium nonylphenoxytetraethyleneoxy sulfate, 16 parts of sodium dodecylbenzene sulfonate, and 20 parts of the condensation product of 0x0 tridecyl alcohol with 15 moles of ethylene oxide, remained clear even when kept at -3 C. overnight. Another composition containing the same amounts of said sulfate ester and said sulfonate, but only 8 parts of the said Oxo tridecyl alcohol condensation product, separated on standing at 2 C. overnight but became clear and homogeneous on returning to room temperature. This invention has been disclosed with respect to certain preferred embodiments, and various modifications and variations thereof will become obvious to the person skilled in the art. It is to be understood that such modifications and variations are to be included within the spirit and purview of this application, and the scope of the appended claims.

We claim: l. A foaming'non-soap detergent composition cornprising,flby Weight, about 25 to 75 parts of a deter'sive water-soluble anionic sulfate ester of a polyoxyethylene derivative of an organic compound of at least 10 carbon atoms, about 75 to 0 parts of a water-soluble anionic alkyl aryl sulfonate detergent containing from 8 to 20 alkyl carbon atoms, and about 10' to of the combined weight of said anionic detergents of a non-ionic surface active polyoxyethylene ether of a multi-branched chain primary aliphatic alcohol of from about 8 to 18 carbon atoms containing about 50 to 90% of combined ethylene oxide, said alcohol having the molecular configuration of an alcohol produced by the x0 process from a multi-branched chain olefin of from 7 to 17 carbon atoms.

2. A composition as defined in claim 1 wherein said multi-branched chain primary aliphatic alcohol is Oxo tridecyl alcohol.

3. A composition as defined in claim 1 wherein said multi-branched chain primary aliphatic alcohol is Oxo decyl alcohol.

4. A composition as defined in claim 2 wherein said anionic ester is the sulfate ester of a polyoxyethylenated alkyl phenol of at least carbon atoms.

5. A composition as defined in claim 2 wherein said alkyl aryl sulfonate is sodium dodecylbenzene sulfonate.

6. A composition as defined in claim 2 wherein said alkyl aryl sulfonate is ammonium dodecylbenzene sulfonate.

7. A composition as defined in claim 2 wherein said non-ionic polyoxyethylene ether contains about 7 to moles of combined ethylene oxide.

8. A composition as defined in claim 3 wherein said anionic ester is the sulfate ester of a polyoxyethylenated alkyl phenol of at least 10 carbon atoms.

9. A composition as defined in claim 3 wherein said alkyl aryl sulfonate is sodium dodecylbenzene sulfonate.

10. A composition as defined in claim 4, wherein said ester is ammonium nonylphenoxytetraethyleneoxy sulfate.

11. A composition as defined in claim 8 wherein said ester is ammonium nonylphenoxytetraethyleneoxy sulfate.

12. A foaming non-soap detergent composition comprising, by weight, about 70 parts of ammonium nonylphenoxytetraethyleneoxy sulfate, and 30 parts of the reaction product of Oxo tridecyl alcohol with from 5 to 15 moles of ethylene oxide.

13. A composition as defined in claim 12 wherein said reaction product contains about 10 moles of combined ethylene oxide.

14. A foaming non-soap detergent composition comprising, by weight, about parts of ammonium nonylphenoxytetraethyleneoxy sulfate, 40 parts of sodium dodecylbenzene sulfonate, and 20 parts of the reaction product of 0x0 tridecyl alcohol with from about 7 to 15 moles of ethylene oxide.

15. A composition as defined in claim 14 wherein said reaction product contains about 15 moles of combined ethylene oxide.

16. A foaming non-soap detergent composition comprising, by weight, about 40 parts of ammonium nonylphenoxytetraethyleneoxy sulfate, 40 parts of sodium dodecylbenzene sulfonate, and 20 parts of the reaction product of 0x0 decyl alcohol with about 14 moles of ethylene oxide.

References Cited in the file of this patent UNITED STATES PATENTS France Mar. 4, 1953 UNITED STATES PATENT OFFICE CERTIFICATION OF CORRECTIQN Patent No. 2,941,951 June 21, 1960 Charles F, Jelinek et al,,

in the above numbered petthat error appears ters Patent should read as It is hereby certified that the said Let ent requiring correction and corrected below.

"anionic" insert organic after 1; least 10 carbon e Column 1, line 22,

taining a sulfate or sulfonate con Signed and sealed this 30th day of May 1961 (SEAL) Attest:

DAVID L. LADD ERNEST W. SDER Attesting Officer Commissioner of Patents 

1. A FOAMING NON-SOAP DETERGENT COMPOSITION COMPRISING, BY WEIGHT , ABOUT 25 TO 75 PARTS OF A DETERSIVE WATER-SOLUABLE ANIONIC SULFATE OF A POLYOXYETHYLENE DERIVATIVE OF AN ORGANIC COMPOUND OF AT LEAST 10 CARBON ATOMS, ABOUT 75 TO 0 PARTS OF A WATER-SOLUBLE ANIONIC ALKYL ARYL SULFONATE DETERGENT CONTAINING FROM 8 TO 20 ALKYL CARBON ATOMS, AND ABOUT 10 TO 90% OF THE COMBINED WEIGHT OF SAID ANIONIC DETERGENTS OF A NON-IONIC SURFACE ACTIVE POLYOXYETHYLENE ETHER OF A MULTI-BRANCHED CHAIN PRIMARY ALIPHATIC ALCOHOL OF FROM ABOUT 8 TO 18 CARBON ATOMS CONTAINING ABOUT 50 TO 90% OF COMBINED ETHYLENE OXIDE, SAID ALCOHOL HAVING THE MOLECULAR CONFIGURATION OF AN ALCOHOL PRODUCED BY THE OXO PROCESS FROM A MULTI-BRANCHED CHAIN OLEFIN OF FROM 7 TO 17 CARBON ATOMS. 